Aminophenolate zinc complex containing pyridine ring as well as preparation method and application thereof

An aminophenoxy zinc, pyridine ring technology, applied in zinc organic compounds, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problem of low catalyst activity, minimal catalyst, poor activity, etc. question

Inactive Publication Date: 2019-06-14
EAST CHINA UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2014, the Du group reported zinc complexes based on chiral aminooxazolines with high stereoselectivity for the polymerization of racemic lactide, and the melting point of the obtained polymers reached T m =214°C, but the catalyst activity is very low (ACS Macro Lett.2014,3,689)
In 2017, the Jones group reported a series of zinc complexes based on aminopiperidine substitutions, which were less active in catalyzing the polymerization of rac-LA
At present, although zinc complexes can effectively catalyze the homopolymerization of LA and ε-CL, there are still very few catalysts that can achieve the copolymerization of LA and ε-CL.

Method used

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  • Aminophenolate zinc complex containing pyridine ring as well as preparation method and application thereof
  • Aminophenolate zinc complex containing pyridine ring as well as preparation method and application thereof
  • Aminophenolate zinc complex containing pyridine ring as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Synthesis of Ligand L1

[0053] (1) Synthesis of N-benzyl-1-(6-methylpyridin-2-yl)methanamine

[0054]

[0055] Add benzylamine (16.07g, 150mmol) and potassium carbonate (1.66g, 12mmol) in the reaction flask, 2-bromomethyl-6-picoline (2.48g, 10mmol) and 25mL N,N-dimethylformamide Afterwards, react for 12 hours. After column chromatography, a red-brown oily liquid (1.02 g, 48%) was obtained.

[0056] (2) Synthesis of Ligand L1

[0057] N-benzyl-1-(6-methylpyridin-2-yl)methanamine (1.22g, 5.73mmol), potassium carbonate (0.95g, 6.87mmol), 2-bromomethyl-4- Methyl-6-tritylphenol (2.54g, 5.73mmol) and 20mL N,N-dimethylformamide were reacted at room temperature for 8 hours. Add water to quench the reaction, extract with ethyl acetate, combine the organic phases, dry over anhydrous magnesium sulfate, filter, evaporate the solvent under reduced pressure, and recrystallize with dichloromethane and petroleum ether to obtain white solid L1 (2.72g, 83%).

[0058]

[0059]...

Embodiment 2

[0061] Synthesis of Ligand L2:

[0062] (1) Synthesis of N-[(6-methylpyridin-2-yl)methyl]n-hexylamine

[0063]

[0064] Except that n-hexylamine (30.36g, 300mmol), potassium carbonate (3.32g, 24mmol) and 2-bromomethyl-6-picoline (3.72g, 20mmol) were used as raw materials, other operating steps were the same as in Example 1. After column chromatography, a red-brown oil (2.03g, 49%) was obtained.

[0065] (2) Synthesis of Ligand L2

[0066] N-[(6-methylpyridin-2-yl)methyl]n-hexylamine (1.10g, 5.35mmol), potassium carbonate (0.89g, 6.42mmol) and 2-bromomethyl-4-methyl -Except for 6-tritylphenol (2.37g, 5.35mmol), other operating steps are the same as in Example 1. Recrystallization from dichloromethane and petroleum ether gave white solid L2 (2.39 g, 79%).

[0067]

[0068] 1 H NMR (CDCl 3 ,400MHz,298K):δ10.67(br s,1H,OH),7.35(dd,1H, 3 J=7.6Hz, 3 J=7.6Hz, PyH), 7.25-7.09(m, 15H, ArH), 6.96(d, 1H, 3 J=7.6Hz,PyH),6.88(d,1H, 4 J=1.6Hz, ArH), 6.80(d, 1H, 4 J=1.6Hz, ArH...

Embodiment 3

[0070] Synthesis of Ligand L3:

[0071] (1) Synthesis of N-[(6-methylpyridin-2-yl)methyl]cyclohexylamine

[0072]

[0073] Except that cyclohexylamine (29.75g, 300mmol), potassium carbonate (3.32g, 24mmol) and 2-bromomethyl-6-picoline (3.72g, 20mmol) were used as raw materials, other operating steps were the same as in Example 1. After column chromatography, a red-brown oil (1.99 g, 48%) was obtained.

[0074] (2) Synthesis of Ligand L3

[0075] N-[(6-methylpyridin-2-yl)methyl]cyclohexylamine (1.55g, 7.59mmol), potassium carbonate (1.27g, 9.14mmol) and 2-bromomethyl-4-methyl Base-6-tritylphenol (3.36g, 7.59mmol), other operating steps are the same as in Example 1. Recrystallization from dichloromethane and petroleum ether gave white solid L3 (3.39 g, 79%).

[0076]

[0077] 1 H NMR (CDCl 3 ,400MHz,298K):δ10.85(br s,1H,OH),7.33(dd,1H, 3 J=7.6Hz, 3 J=7.6Hz, PyH), 7.24-7.09(m, 15H, ArH), 6.93(d, 1H, 3 J=7.6Hz,PyH),6.85(d,1H, 4 J=1.6Hz, ArH), 6.76(d, 1H, 4 J=1.6Hz...

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Abstract

The invention discloses an aminophenolate zinc complex containing pyridine rings, a preparation method of the complex and application of the complex to catalyzing lactone ring opening polymerization.The preparation method of the aminophenolate zinc complex containing pyridine rings comprises the following steps that a neutral ligand directly reacts with a zinc metal raw material compound in an organic medium; then, through the steps of filtering, concentration and recrystallization steps, a target compound is obtained. The aminophenolate zinc complex is an efficient lactone ring opening polymerization catalyst and can be used for catalyzing polymerization reaction of lactone such as lactide and caprolactone; a di-block copolymer can be obtained by catalyzing lactide and caprolactone copolymerization by a one-pot method. The aminophenolate zinc complex has the obvious advantages that the raw materials can be easily obtained; the synthesis route is simple; the product yield is high; high catalytic activity is realized; a high-molecular-weight polyester material can be obtained; the requirements of industrial department can be met. The structure formula is shown in description.

Description

technical field [0001] The invention relates to a class of aminophenol oxyzinc complexes containing pyridine rings and the application of the complexes in lactone polymerization. Background technique [0002] As a class of polymers that can replace traditional petroleum-based polyolefin materials, aliphatic polyesters have attracted extensive attention due to their good biocompatibility and degradability. Among them, polylactic acid is a new type of biodegradable material. It not only comes from renewable resources, but also its waste can be decomposed into carbon dioxide and water through microbial fermentation, which will not pollute the environment, that is, it can be used in nature. Recycling is a recognized environment-friendly green polymer material. At present, it has been widely used in medical materials, drug sustained release and biological tissue engineering and other fields. Polylactic acid polymers with different properties can be obtained by homopolymerizatio...

Claims

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Application Information

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IPC IPC(8): C07D213/38C07D221/04C07F3/06B01J31/18C08G63/08C08G63/83
Inventor 马海燕方超立
Owner EAST CHINA UNIV OF SCI & TECH
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